1. Field of the Invention
This invention relates to selectively adsorbing basic asphaltenes on Bronsted acid catalysts comprising at least one transition metal oxide supported on an alumina support. More particularly, this invention relates to a process for the selective removal of basic asphaltenes from an asphaltene-containing hydrocarbon feed by contacting said feed with a solid, Bronsted acid catalyst comprising at least one transition metal oxide supported on a pyrogenic, .gamma.-alumina support to produce a feed of reduced basic asphaltene content and a catalyst containing basic asphaltenes.
2. Background of the Disclosure
Conventional hydrodesulfurization, hydrodenitrogenation, hydrocracking, cat cracking, reforming and other hydroconversion processes cannot be used on feeds containing appreciable amounts of asphaltene materials due to coking and deactivation off the catalyst by the asphaltenes. Basic asphaltenes are the most troublesome in this regard.
It is known in the art that asphaltenes can be separated into basic and non-basic fractions using mineral acid separation techniques. Basic asphaltenes have been precipitated from various crude oils by potentiometric titration with perchloric acid and there are earlier reports of the use of potentiometric titration to determine basic nitrogen (Nicksic, S. W. and Jeffries-Harris, M. J., Inst. Petrol., 54 (532), 107-114 (1968)). H. Sternberg developed a technique for separating basic and non-basic asphaltenes from coal liquids by first dissolving the asphaltenes in toluene, followed by saturating the solution with anhydrous HCl which precipitates a basic asphaltene-HCl complex from the solution. The precipitate is filtered and the basic asphaltenes are recovered by treating the asphaltene-HCl complex with caustic solution (Sternberg, H. W. Raymond, R., and Schweighardt, F. K., Science, 188, 49 (1975)). In this technique, the non-basic asphaltenes remain in the original toluene solution and are recovered from the filtrate by evaporating off the toluene.
Increasing world petroleum consumption and declining availability of high quality crude oils has forced both producers and refiners of petroleum alike to turn more and more to low quality, heavy crudes having relatively high residuum and concomitant high asphaltene contents. Further, synthetic feeds derived from Alberta Tar Sands, Cole Lake Crude, coal liquids, Venezuelan tar sands and the like also contain appreciable amounts of asphaltenes. Therefore, there is a need for processes which can readily remove at least a portion of the asphaltenes, and particularly the basic asphaltenes, from feeds containing same to permit further processing of the asphaltene-reduced feed into useful products such as chemicals, solvents, fuels and lubricating oils. It would be particularly beneficial if such processes could also make liquid products out of the separated basic asphaltenes.
U.S. Pat. No. 3,691,063 discloses employing solid acid catalysts, such as silica-alumina, in a guard case operated at from 600.degree.-1,000.degree. F. to remove metals and asphaltenes from heavy feeds prior to hydrocracking same. Under these temperature conditions some of the adsorbed asphaltenes are cracked in-situ in the guard case. This in-situ cracking tends to coke the catalyst therein, thereby reducing both its adsorption capacity and selectivity for the basic asphaltenes. U.S. Pat. Nos. 2,944,002 and 2,432,644 disclose the use of solid acid catalysts in guard cases for removing metal and nitrogen-containing catalyst contaminants from feeds being fed to cat crackers. However, none of the processes disclosed in these two patents permits an asphalt-containing feed to be fed to the guard case. In fact, U.S. Pat. No. 2,944,002 repeatedly teaches that the feed going to the guard case must first be deasphalted if it is an asphaltene-containing feed.